JP4189394B2 - CVD method using vertical CVD apparatus - Google Patents

CVD method using vertical CVD apparatus Download PDF

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JP4189394B2
JP4189394B2 JP2005178009A JP2005178009A JP4189394B2 JP 4189394 B2 JP4189394 B2 JP 4189394B2 JP 2005178009 A JP2005178009 A JP 2005178009A JP 2005178009 A JP2005178009 A JP 2005178009A JP 4189394 B2 JP4189394 B2 JP 4189394B2
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processing chamber
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JP2006013490A (en
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廣行 松浦
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東京エレクトロン株式会社
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36Carbonitrides
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/405Oxides of refractory metals or yttrium
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45527Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45531Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45544Atomic layer deposition [ALD] characterized by the apparatus
    • C23C16/45546Atomic layer deposition [ALD] characterized by the apparatus specially adapted for a substrate stack in the ALD reactor
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604Deposition from a gas or vapour
    • H01L21/31637Deposition of Tantalum oxides, e.g. Ta2O5
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/318Inorganic layers composed of nitrides
    • H01L21/3185Inorganic layers composed of nitrides of siliconnitrides

Description

  The present invention relates to a vertical CVD (Chemical Vapor Deposition) apparatus in a semiconductor processing system and a CVD method using the apparatus. Here, in the semiconductor processing, a semiconductor layer, an insulating layer, a conductive layer, and the like are formed in a predetermined pattern on a target substrate such as a wafer, a glass substrate for LCD (Liquid crystal display) or FPD (Flat Panel Display). By this, it means the various processes performed in order to manufacture the structure containing a semiconductor device, the wiring connected to a semiconductor device, an electrode, etc. on this to-be-processed substrate.

  In manufacturing a semiconductor device, a CVD process and a pattern etching process are repeatedly performed on a semiconductor wafer. As semiconductor devices become higher in density and higher in integration, specifications required for CVD processing are becoming stricter year by year. For example, even a very thin oxide film such as a capacitor insulating film or a gate insulating film is required to be further thinned and have high insulating properties.

  A so-called ALD (Atomic Layer Deposition) is known as a technique for improving the quality of a film to be formed with respect to the CVD process. In ALD, by alternately supplying at least two reaction gases in a pulsed manner, a process of adsorbing one reaction gas on a wafer and a process of causing the other reaction gas to act on the adsorbed reaction gas are repeated. In this manner, a film having a predetermined thickness is formed by laminating thin layers formed in each process cycle.

  On the other hand, in the manufacture of semiconductor devices, a vertical heat treatment apparatus that heat-treats a large number of wafers at once is known as an apparatus for performing semiconductor processing on a substrate to be processed, for example, a semiconductor wafer. Usually, a vertical heat treatment apparatus has an airtight vertical processing chamber (reaction tube) for storing wafers. A load port is formed at the bottom of the processing chamber, which is selectively opened and closed by a lid that is raised and lowered by an elevator.

  In the processing chamber, the wafers are held in a state where they are stacked horizontally and spaced from each other by a holder called a wafer boat. The wafer boat is loaded and unloaded into the processing chamber through the load port by the elevator while the wafer is mounted and supported on the lid.

  Patent Document 1 discloses an example of a vertical heat treatment apparatus that performs ALD-type CVD processing. The apparatus disclosed in this publication has a double-pipe structure processing chamber composed of an inner cylinder and an outer cylinder. Each of the two reactive gases supplied alternately is supplied from the bottom of the inner cylinder, passes between the stacked wafers, and then flows from the top of the inner cylinder to the discharge path.

Patent Document 2 and Patent Document 3 disclose another example of a vertical heat treatment apparatus that performs an ALD-type CVD process. The apparatuses disclosed in each of these publications have a processing chamber having a single tube structure, and a buffer chamber common to the two reaction gases is formed in the interior thereof so as to extend in the vertical direction. The buffer chamber has supply holes arranged so as to extend over substantially the entire stacked wafer. The two reaction gases are alternately supplied into the buffer chamber and supplied to the substrate from the supply hole.
US Pat. No. 6,585,823 B1 JP 2003-45864 A JP 2003-297818 A

  As will be described later, according to the present inventor, the above-described conventional apparatus has poor inter-surface uniformity (uniformity between wafers) with respect to characteristics such as quality and thickness of a film formed on a wafer, or reaction. It has been found that there is a problem that productivity is lowered because gas cannot be efficiently exchanged. An object of the present invention is to provide a vertical CVD apparatus in a semiconductor processing system and a CVD method using the apparatus, which can solve at least one of these problems.

A first aspect of the present invention is a vertical CVD apparatus for performing a CVD process on a plurality of substrates to be processed together,
An airtight processing chamber for storing the substrate to be processed;
A holder for holding the substrates to be processed in a stacked state in the processing chamber with a space between each other;
A heater for heating the internal atmosphere of the processing chamber;
An exhaust system for exhausting the processing chamber;
A supply system for supplying a processing gas into the processing chamber, the supply system having a plurality of first supply holes connected to a first reaction gas line for supplying a first reaction gas, and a second supply gas for supplying a second reaction gas. A plurality of second supply holes connected to the two reaction gas lines, and each of the set of the first supply holes and the set of the second supply holes is substantially formed of the stacked substrates to be processed. Arranged vertically next to the edge of the substrate to be processed,
A controller for controlling the operation of the apparatus so as to form a thin film derived from the first and second reaction gases on the substrate to be processed by repeatedly performing the first and second steps; In the first step, by supplying one gas of the first and second reaction gases and stopping the other gas, the one gas is adsorbed on the surface of the substrate to be processed; A step of causing the other gas to act on the one gas adsorbed on the surface of the substrate to be processed by supplying the other gas and stopping the one gas;
It comprises.

A second aspect of the present invention is a vertical CVD apparatus for performing a CVD process on a plurality of substrates to be processed together,
An airtight processing chamber for storing the substrate to be processed;
A holder for holding the substrates to be processed in a stacked state in the processing chamber with a space between each other;
A heater for heating the internal atmosphere of the processing chamber;
An exhaust system for exhausting the processing chamber;
A supply system for supplying a processing gas into the processing chamber, the supply system having a first supply hole connected to a first reaction gas line for supplying a first reaction gas, and a second reaction for supplying a second reaction gas. A plurality of second supply holes connected to a gas line; the first supply holes are disposed substantially at the bottom of the processing chamber; and the second supply holes are stacked. Arranged vertically next to the edge of the substrate to be processed so as to substantially extend over the substrate to be processed;
A controller for controlling the operation of the apparatus so as to form a thin film derived from the first and second reaction gases on the substrate to be processed by repeatedly performing the first and second steps; In the first step, by supplying one gas of the first and second reaction gases and stopping the other gas, the one gas is adsorbed on the surface of the substrate to be processed; A step of causing the other gas to act on the one gas adsorbed on the surface of the substrate to be processed by supplying the other gas and stopping the one gas;
It comprises.

A third aspect of the present invention is a method of performing CVD processing on a plurality of substrates to be processed together in a vertical CVD apparatus,
The device is
An airtight processing chamber for storing the substrate to be processed;
A holder for holding the substrates to be processed in a stacked state in the processing chamber with a space between each other;
A heater for heating the internal atmosphere of the processing chamber;
An exhaust system for exhausting the processing chamber;
A supply system for supplying a processing gas into the processing chamber;
Comprising
The method
A first step of supplying one gas of the first and second reaction gases and stopping the other gas to adsorb the one gas on the surface of the substrate to be processed;
Supplying the other gas and stopping the one gas, thereby causing the other gas to act on the one gas adsorbed on the surface of the substrate to be processed;
Comprising
By repeatedly executing the first and second steps, a thin film derived from the first and second reaction gases is formed on the substrate to be processed.
The first reactive gas is supplied from a plurality of first supply holes arranged in a vertical direction next to an edge of the substrate to be processed so as to substantially cover the stacked substrates to be processed. The two reaction gases are supplied from a plurality of second supply holes arranged in a vertical direction beside an edge of the substrate to be processed so as to substantially cover the stacked substrates to be processed.

A fourth aspect of the present invention is a method of performing a CVD process on a plurality of substrates to be processed together in a vertical CVD apparatus,
The device is
An airtight processing chamber for storing the substrate to be processed;
A holder for holding the substrates to be processed in a stacked state in the processing chamber with a space between each other;
A heater for heating the internal atmosphere of the processing chamber;
An exhaust system for exhausting the processing chamber;
A supply system for supplying a processing gas into the processing chamber;
Comprising
The method
A first step of adsorbing the one gas on the surface of the substrate to be processed by supplying one gas of the first and second reaction gases and stopping the other gas;
Supplying the other gas and stopping the one gas to cause the other gas to act on the one gas adsorbed on the surface of the substrate to be processed;
Comprising
By repeatedly executing the first and second steps, a thin film derived from the first and second reaction gases is formed on the substrate to be processed.
The first reaction gas is supplied from a first supply hole disposed substantially at the bottom of the processing chamber, and the second reaction gas is provided so as to cover substantially the entire substrate to be processed. Supply from a plurality of second supply holes arranged in the vertical direction beside the edge of the substrate to be processed.

  Furthermore, the embodiments of the present invention include inventions at various stages, and various inventions can be extracted by appropriately combining a plurality of disclosed constituent elements. For example, when an invention is extracted by omitting some constituent elements from all the constituent elements shown in the embodiment, when the extracted invention is carried out, the omitted part is appropriately supplemented by a well-known common technique. It is what is said.

  According to the present invention, it is possible to improve inter-surface uniformity with respect to the characteristics of a film formed on a substrate to be processed, or to efficiently exchange a reaction gas.

  In the course of the development of the present invention, the present inventor studied problems in a vertical heat treatment apparatus that performs ALD type CVD processing. As a result, the present invention and the like have obtained knowledge as described below.

  In the case of the apparatus disclosed in Patent Document 1, depending on the processing conditions (temperature, gas flow rate, pressure, time), the wafer closer to the reaction gas introduction side (bottom) tends to have a larger amount of adsorption of molecules of the processing gas. . For this reason, depending on the position of the wafer in the vertical direction, the film quality and the film thickness differ (the inter-surface uniformity is poor). Further, the reaction gas tends to stay between the wafers, and the reaction gas cannot be efficiently exchanged. For this reason, it takes time to purge between the supply pulses of each reaction gas, and productivity is lowered.

  In the case of the devices disclosed in Patent Document 2 and Patent Document 3, the reaction gas tends to remain in a common buffer chamber to which two reaction gases are alternately supplied once. For this reason, there arises a problem that reaction by-products accumulate in the buffer chamber or partially block the supply hole, and gas supply as designed cannot be performed. In order to solve this problem, it is necessary to take time for purging between the supply pulses of each reaction gas, and productivity is lowered.

  Hereinafter, an embodiment of the present invention configured based on such knowledge will be described with reference to the drawings. In the following description, components having substantially the same function and configuration are denoted by the same reference numerals, and redundant description will be given only when necessary.

<First Embodiment>
FIG. 1 is a sectional view showing a CVD apparatus according to the first embodiment of the present invention. FIG. 2 is a plan view of the apparatus shown in FIG. FIG. 3 is an enlarged view of the upper part of the processing chamber of the apparatus shown in FIG. 1 to show the gas flow. The CVD apparatus 2 includes a first gas substantially consisting of a silane-based gas (silicon source gas), a second gas substantially consisting of a nitriding gas, and a third gas substantially consisting of a hydrocarbon gas. The silicon nitride films are formed by alternately supplying the silicon nitride films. As an example, when a silicon nitride film is deposited using, for example, dichlorosilane (DCS: SiH 2 Cl 2 ) and NH 3 , a hydrocarbon gas is supplied to contain a carbon component in the film.

  As shown in FIG. 1, the CVD apparatus 2 includes a cylindrical quartz inner cylinder 4 and a quartz outer cylinder 6 arranged concentrically on the outside via a predetermined gap 10. A processing chamber 8 having a heavy pipe structure is provided. The outside of the processing chamber 8 is covered with a heating cover 16 including a heating means 12 such as a heater and a heat insulating material 14. The heating means 12 is disposed over the entire inner surface of the heat insulating material 14. In the present embodiment, the inner diameter of the inner cylinder 4 of the processing chamber 8 is about 240 mm, the height is about 1300 mm, and the volume of the processing chamber 8 is about 110 liters.

  The lower end of the processing chamber 8 is supported by a cylindrical manifold 18 made of, for example, stainless steel. The lower end of the inner cylinder 4 is supported by a ring-shaped support plate 18 </ b> A that protrudes inward from the inner wall of the manifold 18. A quartz wafer boat 20 on which semiconductor wafers W to be processed are placed in multiple stages is loaded / unloaded from the lower side of the manifold 18 into the processing chamber 8. In the case of the present embodiment, for example, about 100 to 150 wafers having a diameter of 200 mm can be supported on the web boat 20 in multiple stages at substantially equal pitches. Note that the size and number of wafers W are not limited to this, and can be applied to a wafer having a diameter of 300 mm, for example.

  The wafer boat 20 is placed on the rotary table 24 via a quartz heat insulating cylinder 22. The rotary table 24 is supported on a rotary shaft 28 that passes through a lid portion 26 that opens and closes a lower end opening of the manifold 18. For example, a magnetic fluid seal 30 is interposed in the penetrating portion of the rotary shaft 28, and the rotary shaft 28 is rotatably supported in a state of being hermetically sealed. Further, a sealing member 32 made of, for example, an O-ring is interposed between the peripheral portion of the lid portion 26 and the lower end portion of the manifold 18 to maintain the sealing performance in the processing chamber 8.

  The rotating shaft 28 is attached to the tip of an arm 36 supported by a lifting mechanism 34 such as a boat elevator. The wafer boat 20 and the lid portion 26 are moved up and down integrally by the lifting mechanism 34. An exhaust port 38 for discharging the atmosphere in the processing chamber 8 from the bottom of the gap 10 between the inner cylinder 4 and the outer cylinder 6 is formed on the side of the manifold 18. The exhaust port 38 is connected to a vacuum exhaust unit 39 having a vacuum pump or the like.

  A gas supply unit 40 for supplying a predetermined processing gas into the inner cylinder 4 is disposed on the side of the manifold 18. Specifically, the gas supply unit 40 includes a silane-based gas supply system 42, a nitriding gas supply system 44, and a hydrocarbon gas supply system 46. Each gas supply system 42, 44, 46 has gas nozzles 48, 50, 52 provided so as to penetrate the side wall of the manifold 18 side by side in the horizontal direction. For convenience, in FIG. 1, the gas nozzles 48, 50, 52 are shown as penetrating through the side walls of the manifold 18 in the vertical direction.

  Each gas nozzle 48, 50, 52 is bent at a right angle at the bottom of the processing chamber 8 and extends vertically along the wafer boat 20 to the top. The gas nozzles 48, 50, 52 pass through the side wall of the manifold 18 side by side in the horizontal direction, and their vertical portions are also arranged along the periphery of the wafer boat 20 as shown in FIG. 2. As shown in FIG. 3, a large number of supply holes 53 for supplying a processing gas are formed in the vertical portions of the gas nozzles 48, 50, and 52. The supply holes 53 are arranged vertically next to the edges of the wafers W so as to substantially cover the entire stacked wafers W.

Each gas nozzle 48, 50, 52 is connected to a gas flow path 60, 62, 64 having a flow rate controller 54, 56, 58 such as a mass flow controller and a switching valve 55, 57, 59, respectively. The The gas flow paths 60, 62, and 64 are configured such that silane-based gas, nitriding gas, and hydrocarbon gas can be supplied while controlling the flow rate. Here, for example, DCS gas is used as the silane-based gas, NH 3 gas is used as the nitriding gas, and ethylene (C 2 H 4 ) gas is used as the hydrocarbon gas.

The gas supply unit 40 includes an inert gas supply system 72 that supplies an inert gas (used as a carrier gas or a purge gas). The inert gas supply system 72 has inert gas lines 76a, 76b, and 76c that are individually connected to the gas flow paths 60, 62, and 64, respectively. In each of the inert gas lines 76a, 76b, and 76c, flow rate controllers 74a, 74b, and 74c such as a mass flow controller and switching valves 75a, 75b, and 75c are provided, respectively. For example, N 2 or Ar is used as the inert gas.

  That is, in the apparatus of the first embodiment, the gas supply systems 42, 44, 46 have gas nozzles 48, 50, 52 that can selectively or simultaneously supply the corresponding reaction gas and inert gas, respectively. Each nozzle 48, 50, 52 is formed with a supply hole 53 arranged in a vertical direction beside the edge of the wafer W so as to substantially cover the entire stacked wafer W. On the other hand, around the wafer W, there is an inner exhaust passage 9 extending vertically along the edge of the wafer W so as to extend substantially along the inner surface of the inner cylinder 4. It is formed. The inner exhaust path 9 communicates with a gap (outer exhaust path) 10 between the inner cylinder 4 and the outer cylinder 6 connected to the vacuum exhaust part 39 at the upper end portion of the inner cylinder 4.

  Next, a CVD method performed using the apparatus configured as described above will be described. Note that the method described below (including gas supply and stoppage) is performed in accordance with a CVD process recipe stored in advance in the storage unit 5 s of the CPU 5, for example, according to the film thickness of the silicon nitride film to be formed. be able to. In the storage unit 5s, the relationship between the processing gas flow rate and the silicon nitride film thickness is stored in advance as control data. Therefore, the CPU 5 can control the gas supply unit 40 and the like based on these stored processing recipes and control data.

  First, when the CVD apparatus is in a standby state in which no wafer is loaded, the inside of the processing chamber 8 is maintained at a processing temperature, for example, about 550 ° C. On the other hand, a room temperature wafer boat 20 on which a large number of, for example, 100 wafers W are mounted is lifted into the processing chamber 8 from below and loaded into the processing chamber 8. Then, the inside of the processing chamber 8 is sealed by closing the lower end opening of the manifold 18 with the lid 26.

  Next, the inside of the processing chamber 8 is evacuated to maintain a predetermined processing pressure, and the wafer temperature is raised to a film forming processing temperature. After the temperature is stabilized, each nozzle 48, 50, 52 of the gas supply unit 40 is controlled while the flow rate of DCS gas, which is a predetermined silane-based gas, ammonia gas, which is a nitriding gas, and ethylene gas, which is a hydrocarbon gas, is controlled. Supply from. At this time, a silicon nitride film is formed using a gas supply pattern as described below. Note that the inside of the processing chamber 8 is evacuated over the entire period of film formation.

FIG. 4 is a timing chart showing a gas supply pattern according to the first embodiment of the present invention. As shown in FIG. 4, the supply timings of the three kinds of reaction gases, that is, the supply timings are different from each other. That is, one cycle of supplying DCS gas (T1), then supplying NH 3 gas (T3), and finally supplying C 2 H 4 gas (T5) is continuously performed a plurality of times. Between the gas supply periods T1, T3, and T5, intermittent periods T2, T4, and T6 are provided in which all three types of reaction gases are stopped and purged with an inert gas.

The flow rate of DCS gas is 50 to 2000 sccm, for example 300 sccm, the flow rate of NH 3 gas is 150 to 5000 sccm, for example 1000 sccm, and the flow rate of C 2 H 4 gas is 50 to 2000 sccm, for example 500 sccm. The processing temperature is constant at 450 to 600 ° C., for example, 550 ° C., and the processing pressure is 13 Pa to 1.33 kPa for the gas supply periods T1, T3, and T5, for example, 133 Pa (1 Torr), and 13 for the intermittent periods T2, T4, and T6. ~ 133 Pa, for example 40 Pa (0.3 Torr). One (one pulse) gas supply periods T1, T3, and T5 are 15 to 60 seconds, and intermittent periods T2, T4, and T6 are 30 to 180 seconds. For example, if the gas supply period is 30 seconds and the intermittent period is 30 seconds, the length of one cycle T1 to T6 is about 3 minutes.

In each cycle T1 to T6, the process proceeds on the surface of the wafer W as follows. That is, the DCS gas is adsorbed on the surface of the wafer W in the first supply period T1 in which the DCS gas that is the first reaction gas is supplied. In the second supply period T3 in which the NH 3 gas as the second reaction gas is supplied, the NH 3 gas acts on the DCS gas adsorbed on the surface of the wafer W, and the unit layer made of silicon nitride is formed on the surface of the wafer W Formed. Then, the third is the reaction gas C 2 H 4 third supply period for supplying the gas T5, and silicon nitride bonded cleavage π of C 2 H 4 C = C double bond of the gas reaction The carbon component is contained in the unit layer made of silicon nitride. In this way, the carbon unit-containing silicon nitride film having a predetermined thickness is formed by laminating the thin unit layers formed in each cycle T1 to T6.

In the intermittent periods T2, T4, and T6, unnecessary gas is discharged from the surface of the wafer W by purging with an inert gas. Since the inside of the processing chamber 8 is evacuated over the entire film formation period T1 to T6, the supply of the three types of gases is stopped, and as an inert gas from the supply holes 53 of the nozzles 48, 50, and 52, for example, A purge process can be performed by supplying only N 2 gas. Note that only the evacuation of the processing chamber 8 may be continued without supplying the inert gas.

In this way, when the silicon nitride film is formed, a carbon component is contained in the silicon nitride film formed on the wafer surface by supplying, for example, C 2 H 4 gas as a hydrocarbon gas into the processing chamber 8. It will be in the state. As a result, etching with respect to dilute hydrofluoric acid used at the time of the cleaning process or etching process of the surface of the silicon nitride film, despite the film formation at a temperature lower than the conventional film formation temperature, for example, about 760 ° C., for example, 550 ° C. The rate can be reduced. As a result, it is possible to prevent the silicon nitride film from being excessively scraped off during the cleaning process and to improve the controllability of the film thickness. Further, the silicon nitride film can sufficiently function as an etching stopper film.

The intermittent periods T2, T4, and T6 function as a modification period that improves the quality of the film formed on the surface of the wafer W. The reforming action during the intermittent period is considered to proceed as follows. That is, when a silicon nitride film containing carbon atoms is formed, Cl atoms that could not be desorbed during deposition in the DCS gas are bonded in an activated state to the outermost surface of the thin film. In the intermittent period in which the supply of DCS gas is stopped, C atoms and N atoms in C 2 H 4 gas and NH 3 gas are replaced with Cl atoms on the outermost surface of the thin film, and the Cl component in the film is reduced. As a result, the etching rate decreases. In particular, when C 2 H 4 gas is used, the amount of C atoms taken into the silicon nitride film increases, so that the etching rate can be further suppressed.

  In the apparatus of the first embodiment, in the gas supply periods T1, T3, and T5, each of the three types of gas is forcibly and horizontally forced from the supply holes 53 of the corresponding nozzles 48, 50, and 52 between the wafers W. (See arrow A1 in FIG. 3). In addition, in the intermittent periods T2, T4, and T6 that function as the purge period, the inert gas is forcibly almost horizontally sent from the supply holes 53 of the corresponding nozzles 48, 50, and 52 between the wafers W (FIG. 3, FIG. 3). (See arrow A1). Under the action of the evacuation unit 39, these supplied gases are discharged upward between the wafers W along the inner exhaust path 9 extending vertically along the edge of the wafer W (FIG. 3, arrow A2). reference).

  By supplying and discharging such gas, the reaction gas can be supplied uniformly to all the wafers W regardless of the position of the wafer W in the vertical direction. Therefore, the inter-surface uniformity (uniformity between wafers) is improved with respect to characteristics such as the quality and thickness of the film formed on the wafer W. Further, the reaction gas exchange on the surface of the wafer W can be efficiently performed by forcibly supplying the gas between the wafers W. Therefore, the purge period (intermittent period) can be shortened to shorten the cycles T1 to T6, and the productivity is improved accordingly.

  Further, since the inert gas is supplied through the nozzles 48, 50, 52, it is possible to prevent the by-products from depositing in the nozzles 48, 50, 52 and the supply holes 53. From this point of view, in the purge period, the inert gas may be supplied only from the nozzle to which the reaction gas is supplied at least immediately before, and the supply of the inert gas from other nozzles is optional.

Second Embodiment
FIG. 5 is a cross-sectional view showing a processing chamber of the CVD apparatus according to the second embodiment of the present invention. 6 is an enlarged view of the upper part of the processing chamber of the apparatus shown in FIG. 5 and shows the gas flow. This apparatus is also configured to form a silicon nitride film by alternately supplying DCS gas, which is a silane-based gas, ammonia gas, which is a nitriding gas, and ethylene gas, which is a hydrocarbon gas.

  The device shown in FIG. 5 is similar to the device shown in FIG. 1, but has a different configuration with respect to the exhaust system. As shown in FIGS. 5 and 6, a plurality of exhaust holes 81 are formed in the wall of the inner cylinder 4 </ b> X on the second side facing the first side where the supply holes 53 of the gas nozzles 48, 50, 52 are arranged. . The exhaust holes 81 are arranged vertically next to the edge of the wafer W so as to substantially cover the entire stacked wafer W. The exhaust hole 81 communicates with a gap (outer exhaust path) 10 between the inner cylinder 4 </ b> X and the outer cylinder 6 connected to the vacuum exhaust part 39. The top of the inner cylinder 4X is completely closed by the top plate 80 so that gas does not flow out.

  The CVD method performed using the apparatus shown in FIG. 5 is substantially the same as that described with reference to the apparatus shown in FIG. The gas supply pattern at this time is as shown in the timing chart of FIG. In the apparatus shown in FIG. 5 as well, the gas from the supply holes 53 of the gas nozzles 48, 50, and 52 is forcibly sent between the wafers W substantially horizontally (see arrow A5 in FIG. 6). On the other hand, the supplied gas is sucked into the exhaust hole 81 substantially horizontally from between the wafers W under the action of the vacuum exhaust part 39 and discharged to the outer exhaust path 10 (see arrow A6 in FIG. 6).

  By supplying and discharging such gas, the apparatus shown in FIG. 5 can obtain the following effects in addition to the effects of the apparatus shown in FIG. That is, since the gas between the wafers W is sucked in substantially parallel to the surface of the wafer W by the exhaust holes 81, a uniform laminar flow is easily formed from one end to the other end on the surface of each wafer W. Therefore, in-plane uniformity (uniformity on the surface of each wafer) is improved with respect to characteristics such as the quality and thickness of the film formed on each wafer W. Further, since the exhaust holes 81 are arranged adjacent to the edge of the wafer W, gas can be discharged from between the wafers W more efficiently. Therefore, the purge period (intermittent period) can be shortened to shorten the cycles T1 to T6, and the productivity is improved accordingly.

<Third Embodiment>
FIG. 7 is a cross-sectional view showing a processing chamber of a CVD apparatus according to the third embodiment of the present invention. FIG. 8 is a plan view of the apparatus shown in FIG. This apparatus is also configured to form a silicon nitride film by alternately supplying DCS gas, which is a silane-based gas, ammonia gas, which is a nitriding gas, and ethylene gas, which is a hydrocarbon gas.

  The apparatus shown in FIG. 7 is similar to the apparatus shown in FIG. 5, but the processing chamber 8 </ b> X does not have an inner cylinder and is composed of a single cylinder. In the processing chamber 8X, the vertically extending gas nozzles 48, 50, 52 and the vertically extending flat exhaust pipe 85 are opposed to each other with the stacked wafers W sandwiched therebetween (thus, with the wafer boat 20 sandwiched). Arranged. The exhaust pipe 85 is defined by a casing 87 hermetically welded onto the inner surface of a quartz cylinder, and a plurality of exhaust holes 86 are formed in the wall facing the wafer W. The exhaust holes 86 are arranged vertically next to the edge of the wafer W so as to substantially cover the entire stacked wafer W.

  In the apparatus shown in FIG. 7, the processing chamber 8 </ b> X has a single cylinder structure, but it is possible to obtain substantially the same operations and effects as those of the apparatus shown in FIG. 5.

<Fourth embodiment>
FIG. 9 is a cross-sectional view showing a processing chamber of a CVD apparatus according to the fourth embodiment of the present invention. This apparatus is also configured to form a silicon nitride film by alternately supplying DCS gas, which is a silane-based gas, ammonia gas, which is a nitriding gas, and ethylene gas, which is a hydrocarbon gas.

  The apparatus shown in FIG. 9 is similar to the apparatus shown in FIG. 5, but an exhaust port 38 </ b> X for discharging the atmosphere in the processing chamber 8 is formed at the top of the outer cylinder 6. The exhaust port 38X is connected to a vacuum exhaust unit 39 having a vacuum pump or the like via a pipe passing through the top of the heating cover 16 (see FIG. 1). Thus, by arranging the exhaust port 38X of the processing chamber 8 at the top, the entire apparatus can be compactly gathered. In addition, the apparatus shown in FIG. 9 can obtain substantially the same operations and effects as those of the apparatus shown in FIG.

<Common items of the first to fourth embodiments>
The order of supply of the reaction gas shown in the timing chart of FIG. 4 is an example, and can be arbitrarily changed. However, for a substrate to be processed having a silicon surface, it is desirable to protect this by first supplying a processing gas containing C to form Si—C bonds on the silicon surface. That is, it is desirable to first flow DCS gas alone (or simultaneously with C 2 H 4 gas) and then flow NH 3 gas. If NH 3 gas is flowed first, an N—Si bond having low chemical resistance (easy to be etched) is formed on the wafer surface. In order to prevent this, a DCS gas and / or a C 2 H 4 gas is first flowed to form a Si—C bond having strong chemical resistance (not easily etched).

C 2 H 4 (ethylene) is exemplified as a hydrocarbon gas for containing a carbon component in the silicon nitride film. In this regard, as the hydrocarbon gas, one or more gases selected from the group consisting of acetylene, ethylene, methane, ethane, propane, and butane can be used. For example, when ethane is used as the hydrocarbon gas, it is preferably supplied into the processing chamber 8 after being preheated to about 500 to 1000 ° C.

C 2 H 4 gas, which is a hydrocarbon gas, is used to reduce the etching rate of the silicon nitride film with respect to dilute hydrofluoric acid. Therefore, depending on the use of the silicon nitride film, it is not necessary to supply the hydrocarbon gas, that is, the hydrocarbon gas supply system 46 (see FIG. 1) is unnecessary. In this case, in the timing chart of FIG. 4, one cycle for forming the unit layer of the silicon nitride film is composed of periods T1 to T4.

Dichlorosilane (DCS) is exemplified as the silane-based gas for forming the silicon nitride film. In this regard, monosilane (SiH 4 ), disilane (Si 2 H 6 ), trichlorosilane (SiHCl 3 ) are suitable as the silane-based gas for forming the silicon nitride film, which is suitable for the apparatuses according to the first to fourth embodiments. ), Tetrachlorosilane (SiCl 4 ), and binary butylaminosilane (BTBAS) can be used.

The apparatus according to the first to fourth embodiments can also be applied when forming a film other than a silicon nitride film. One example is when an alumina (Al 2 O 3 ) film is formed. In this case, an organometallic gas containing aluminum such as Al (CH 3 ) 3 is used as the first reaction gas, and an oxidizing gas such as O 2 , O 3 , and H 2 O is used as the second reaction gas. .

  In the apparatus according to the first to fourth embodiments, since all the gas nozzles 48, 50, 52 extend to the uppermost wafer W, the type of reaction gas flowing through these must be considered. That is, when the reaction gas has a low bond dissociation energy (easily decomposes) or has a low vapor pressure (it is difficult to supply gas evenly to the top), a nozzle that is long in the vertical direction is not suitable. From this point of view, it is desirable that the gas used in the gas nozzles 48, 50, and 52 has a vapor pressure of 2.66 kPa or higher, a bond dissociation energy of 250 kJ / mol or higher, and a vapor pressure of 4 kPa or higher. It is more desirable that the energy is 300 kJ / mol or more.

<Fifth Embodiment>
FIG. 10 is a sectional view showing a CVD apparatus according to the fifth embodiment of the present invention. 11 is an enlarged view of the upper part of the processing chamber of the apparatus shown in FIG. 10 and shows the gas flow. The CVD apparatus 102 is configured to alternately supply a first gas substantially made of an organometallic gas containing tantalum and a second gas substantially made of an oxidizing gas to form a tantalum oxide film. . As an example, a tantalum oxide film (Ta 2 O 5 ) is deposited using a metal alkoxide of tantalum, for example, Ta (OC 2 H 5 ) 5 (pentaethoxytantalum: PET) gas and H 2 O gas (water vapor). .

  The apparatus shown in FIG. 10 is similar to the apparatus shown in FIG. 1, but the gas supply unit and the control system are greatly different because the deposited films are different. That is, a gas supply unit 140 for supplying a predetermined processing gas into the inner cylinder 4 is disposed on the side of the manifold 18. Specifically, the gas supply unit 140 includes an organometallic gas supply system 142 and an oxidizing gas supply system 144. Each of the gas supply systems 142 and 144 includes gas nozzles 148 and 150 that are arranged in the horizontal direction so as to penetrate the side wall of the manifold 18. For convenience, the gas nozzles 148 and 150 are shown in FIG. 10 so as to penetrate the side wall of the manifold 18 in the vertical direction.

  A gas nozzle 148 that supplies PET as an organometallic gas opens upward at the bottom of the processing chamber 8. The gas nozzle 150 that supplies water vapor as an oxidizing gas is bent at a right angle at the bottom of the processing chamber 8 and extends vertically along the wafer boat 20 to the top. As shown in FIG. 11, a number of supply holes 153 for supplying a processing gas are formed in the vertical portion of the gas nozzle 150. The supply holes 153 are arranged in the vertical direction next to the edge of the wafer W so as to substantially extend over the stacked wafers W.

  Gas flow paths 160 and 162 having flow rate controllers 154 and 156 such as mass flow controllers and switching valves 155 and 157 are connected to the gas nozzles 148 and 150, respectively. The gas flow paths 160 and 162 are configured so that an organometallic gas and an oxidizing gas can be supplied while controlling their flow rates. Here, for example, PET gas is used as the organometallic gas, and water vapor is used as the oxidizing gas.

The gas supply unit 140 includes an inert gas supply system 72 that supplies an inert gas (used as a carrier gas or a purge gas). The inert gas supply system 72 includes inert gas lines 76 a and 76 b that are individually connected to the gas flow paths 160 and 162. The inert gas lines 76a and 76b are respectively provided with flow rate controllers 74a and 74b such as a mass flow controller and switching valves 75a and 75b. For example, N 2 or Ar is used as the inert gas.

  That is, in the apparatus according to the fifth embodiment, the gas supply systems 142 and 144 include gas nozzles 148 and 150 that can selectively or simultaneously supply the corresponding reaction gas and inert gas, respectively. The gas nozzle 148 is provided with a supply hole that opens upward at the bottom of the processing chamber 8. The gas nozzle 150 is formed with supply holes 153 arranged in the vertical direction next to the edge of the wafer W so as to substantially cover the entire stacked wafer W. On the other hand, around the wafer W, there is an inner exhaust passage 9 extending vertically along the edge of the wafer W so as to extend substantially along the inner surface of the inner cylinder 4. It is formed. The inner exhaust path 9 communicates with a gap (outer exhaust path) 10 between the inner cylinder 4 and the outer cylinder 6 connected to the vacuum exhaust part 39 at the upper end portion of the inner cylinder 4.

  Next, a CVD method performed using the apparatus configured as described above will be described. Note that the method described below (including supply and stop of gas) is performed according to a CVD process recipe, for example, a film thickness of a tantalum oxide film to be formed, which is stored in advance in the storage unit 5 s of the CPU 5. be able to. In the storage unit 5s, the relationship between the processing gas flow rate and the film thickness of the tantalum oxide film is stored in advance as control data. Therefore, the CPU 5 can control the gas supply unit 140 and the like based on these stored processing recipes and control data.

  First, when the CVD apparatus is in a standby state in which no wafer is loaded, the inside of the processing chamber 8 is maintained at a processing temperature, for example, about 300 ° C. On the other hand, a room temperature wafer boat 20 on which a large number of, for example, 100 wafers W are mounted is lifted into the processing chamber 8 from below and loaded into the processing chamber 8. Then, the inside of the processing chamber 8 is sealed by closing the lower end opening of the manifold 18 with the lid 26.

  Next, the inside of the processing chamber 8 is evacuated to maintain a predetermined processing pressure, and the wafer temperature is raised to a film forming processing temperature. After the temperature is stabilized, PET gas, which is a predetermined organometallic gas, and water vapor, which is an oxidizing gas, are supplied from the nozzles 148 and 150 of the gas supply unit 140 while controlling the flow rates. At this time, a tantalum oxide film is formed using a gas supply pattern as described below. Note that the inside of the processing chamber 8 is evacuated over the entire period of film formation.

FIG. 12 is a timing chart showing a gas supply pattern according to the fifth embodiment of the present invention. As shown in FIG. 12, the supply timings of the two types of reaction gases, that is, the supply timings are different from each other. That is, one cycle of supplying water vapor (T11) and then supplying PET gas (T13) is continuously performed a plurality of times. The PET gas is supplied with an inert gas such as N 2 gas as a carrier gas. Between the gas supply periods T11 and T13, intermittent periods T12 and T14 are provided in which all of the two kinds of reaction gases are stopped and purged with an inert gas.

The flow rate of water vapor is 10 to 1000 sccm, the flow rate of PET gas is about 0.05 to 5.0 ml / min in terms of PET liquid, and the flow rate of N 2 gas as a carrier gas is 1000 sccm. The processing temperature is constant at 200 to 450 ° C., and the processing pressure is 13 to 133 Pa in the gas supply periods T11 and T13, and 13 to 133 Pa in the intermittent periods T12 and T14. One (one pulse) gas supply period T11, T13 is 60 to 120 seconds, and intermittent period T12, T14 is 30 to 60 seconds. Therefore, for example, if the gas supply period is 60 seconds and the intermittent period is 30 seconds, the length of one cycle T11 to T14 is about 3 minutes.

  In each cycle T11 to T14, the process proceeds on the surface of the wafer W as follows. That is, water vapor is adsorbed on the surface of the wafer W in the first supply period T11 in which water vapor that is the first reaction gas is supplied. In the second supply period T13 in which the PET gas as the second reaction gas is supplied, the PET gas acts on the water vapor adsorbed on the surface of the wafer W, and a unit layer made of tantalum oxide is formed on the surface of the wafer W. The In this manner, a tantalum oxide film having a predetermined thickness is formed by laminating thin unit layers formed in each cycle T11 to T14.

In the intermittent periods T12 and T14, unnecessary gas is discharged from the surface of the wafer W by purging with an inert gas. Since the inside of the processing chamber 8 is evacuated over the entire film formation period T11 to T14, the supply of the two kinds of gases is stopped and an inert gas such as N 2 is supplied from the supply holes 153 of the nozzles 148 and 150. The purge process can be performed by supplying only the gas. Note that only the evacuation of the processing chamber 8 may be continued without supplying the inert gas.

  Thus, by forming a thin unit layer by laminating, it is possible to provide a tantalum oxide film having good surface properties and excellent electrical characteristics. Here, the intermittent periods T12 and T14 function as a modification period for improving the quality of the film formed on the surface of the wafer W.

  In the apparatus of the fifth embodiment, during the gas supply period T11, water vapor is forcibly sent from the supply hole 153 of the nozzle 150 between the wafers W substantially horizontally (see arrow A11 in FIG. 11). In addition, in the intermittent period T12 functioning as a purge period, the inert gas is forcibly sent from the supply hole 153 of the nozzle 150 to the wafer W substantially horizontally (see arrow A11 in FIG. 11). Under the action of the vacuum exhaust part 39, these supplied gases are exhausted upward between the wafers W along the inner exhaust path 9 extending vertically along the edge of the wafer W (FIG. 11, arrow A12). reference).

  By supplying and discharging such gas, it is possible to supply water vapor uniformly to all the wafers W regardless of the vertical position of the wafers W. Therefore, the inter-surface uniformity (uniformity between wafers) is improved with respect to characteristics such as the quality and thickness of the film formed on the wafer W. Further, the reaction gas exchange on the surface of the wafer W can be efficiently performed by forcibly supplying the gas between the wafers W. Therefore, the purge period (intermittent period) can be shortened to shorten the cycles T11 to T4, and the productivity is improved accordingly.

  On the other hand, the PET gas having a low bond dissociation energy is supplied from the supply hole of the nozzle 148 opened at the bottom of the processing chamber 8. The PET gas flows between the wafers W while moving upward under the action of the vacuum exhaust unit 39. Since the nozzle 148 has substantially no vertical portion that is affected by heat in the processing chamber 8, it is unlikely that the PET gas will decompose (cause byproduct deposition) in the nozzle 148.

  Further, since the inert gas is supplied through the nozzles 148 and 150, it is possible to prevent the by-products from being accumulated in the nozzles 148 and 150 and the supply holes 153. From this point of view, in the purge period, the inert gas may be supplied only from the nozzle to which the reaction gas is supplied at least immediately before, and the supply of the inert gas from other nozzles is optional.

<Sixth Embodiment>
FIG. 13 is a cross-sectional view showing a processing chamber of a CVD apparatus according to the sixth embodiment of the present invention. 14 is an enlarged view of the upper part of the processing chamber of the apparatus shown in FIG. 13 and shows the gas flow. This apparatus is also configured to alternately supply PET gas, which is an organometallic gas containing tantalum, and water vapor, which is an oxidizing gas, to form a tantalum oxide film.

  The device shown in FIG. 13 is similar to the device shown in FIG. 10, but has a different configuration with respect to the exhaust system. As shown in FIGS. 13 and 14, an exhaust port 38 </ b> X for discharging the atmosphere in the processing chamber 8 is formed at the top of the outer cylinder 6. The exhaust port 38X is connected to a vacuum exhaust part 39 having a vacuum pump or the like through a pipe penetrating the top of the heating cover 16 (see FIG. 11).

  A plurality of exhaust holes 81 are formed in the wall of the inner cylinder 4X on the second side opposite to the first side where the supply holes 153 of the gas nozzle 150 are arranged. The exhaust holes 81 are arranged vertically next to the edge of the wafer W so as to substantially cover the entire stacked wafer W. The exhaust hole 81 communicates with a gap (outer exhaust path) 10 between the inner cylinder 4 </ b> X and the outer cylinder 6 connected to the vacuum exhaust part 39. The top of the inner cylinder 4X is completely closed by the top plate 80 so that gas does not flow out.

  The CVD method performed using the apparatus shown in FIG. 13 is substantially the same as that described with reference to the apparatus shown in FIG. The gas supply pattern at this time is as shown in the timing chart of FIG. In the apparatus shown in FIG. 13 as well, the gas from the supply hole 153 of the gas nozzle 150 is forcibly fed horizontally between the wafers W (see FIG. 14, arrow A15). Further, the gas from the supply hole of the nozzle 148 flows between the wafers W while moving upward from the bottom of the processing chamber 8. On the other hand, the supplied gas is sucked into the exhaust hole 81 substantially horizontally from between the wafers W under the action of the vacuum exhaust part 39 and discharged to the outer exhaust path 10 (see arrow A16 in FIG. 14).

  By supplying and discharging such gas, the apparatus shown in FIG. 13 can obtain the following effects in addition to the effects of the apparatus shown in FIG. That is, since the gas between the wafers W is sucked in substantially parallel to the surface of the wafer W by the exhaust holes 81, a uniform laminar flow is easily formed from one end to the other end on the surface of each wafer W. Therefore, in-plane uniformity (uniformity on the surface of each wafer) is improved with respect to characteristics such as the quality and thickness of the film formed on each wafer W. Further, since the exhaust holes 81 are arranged adjacent to the edge of the wafer W, gas can be discharged from between the wafers W more efficiently. Therefore, the purge period (intermittent period) can be shortened to shorten the cycles T11 to T14, and the productivity is improved accordingly.

<Seventh embodiment>
FIG. 15 is a sectional view showing a processing chamber of a CVD apparatus according to the seventh embodiment of the present invention. 16 is a plan view of the apparatus shown in FIG. This apparatus is also configured to alternately supply PET gas, which is an organometallic gas containing tantalum, and water vapor, which is an oxidizing gas, to form a tantalum oxide film.

  The apparatus shown in FIG. 15 is similar to the apparatus shown in FIG. 13, but the processing chamber 8 </ b> X does not have an inner cylinder and is composed of a single cylinder. In the processing chamber 8X, a vertically extending gas nozzle 150 and a vertically extending flat exhaust pipe 85 are disposed so as to face each other with the stacked wafers W sandwiched therebetween (and thus with the wafer boat 20 sandwiched therebetween). . The exhaust pipe 85 is defined by a casing 87 hermetically welded onto the inner surface of a quartz cylinder, and a plurality of exhaust holes 86 are formed in the wall facing the wafer W. The exhaust holes 86 are arranged vertically next to the edge of the wafer W so as to substantially cover the entire stacked wafer W.

  In the apparatus shown in FIG. 15, the processing chamber 8 </ b> X has a single cylinder structure, but it is possible to obtain substantially the same operations and effects as those of the apparatus shown in FIG. 13.

<Common Items of Fifth to Seventh Embodiments>
The order of the reactant gas supply shown in the timing chart of FIG. 12 is an example, and this may be reversed. PET is exemplified as the organometallic gas for forming the tantalum oxide film. Other organometallic gases containing tantalum, such as TBTDET (tris-diethylamino-tert-butylimino tantalum: (C 4 H 10 N) 3 Ta (NC 4 H 9 )) can also be used. Moreover, although water vapor is illustrated as an oxidizing gas for forming the tantalum oxide film, other oxidizing gases such as O 2 and O 3 can also be used.

The devices according to the fifth to seventh embodiments can also be applied when forming a film other than a tantalum oxide film. For example, one example is a process for forming a silicon nitride film by supplying a silane-based gas having a low bond dissociation energy such as hexachlorodisilane (HCD: Si 2 Cl 6 ) gas and NH 3 gas. In this case, the silane-based gas is supplied from the nozzle 148 and the NH 3 gas is supplied from the nozzle 150. Other examples are TDMAH (tetrakis (dimethylamino) hafnium: Hf [N (CH 3 ) 2 ] 4 ) or TEMAH (tetrakis (ethylmethylamino) hafnium: Hf [N (CH 3 ) (C 2 H 5 )] 4 ) gas. And an oxidizing gas are supplied to form a hafnium oxide (HfOx) film. In this case, TDMAH or TEMAH gas is supplied from the nozzle 148, and oxidizing gas is supplied from the nozzle 150.

The devices according to the fifth to seventh embodiments can be widely applied to the case where other films are formed. For example, in these examples, the process of forming a silicon nitride film by supplying a silane-based gas and a nitriding gas described in the first to fourth embodiments, and supplying an organometallic gas containing aluminum and an oxidizing gas are provided. This is a process for forming an alumina (Al 2 O 3 ) film. In these cases, it is desirable to supply a gas that is easily decomposed or has a low vapor pressure from a short nozzle 148.

  In summary, the devices according to the fifth to seventh embodiments are suitably applied when the conditions such as bond dissociation energy and vapor pressure of the two reaction gases used are greatly different. That is, when the reaction gas has a low bond dissociation energy (easily decomposes) or has a low vapor pressure (it is difficult to supply the gas evenly to the top), the nozzle 150 that is long in the vertical direction is not suitable. Therefore, a reactive gas having a vapor pressure of 1.33 kPa or less or a bond dissociation energy of 250 kJ / mol or less is supplied from a short nozzle 148. On the other hand, a reactive gas that satisfies the conditions of vapor pressure or bond dissociation energy as described in the common matters of the first to fourth embodiments is supplied from a long nozzle 150.

  In addition, in the category of the idea of the present invention, those skilled in the art can conceive of various changes and modifications, and it is understood that these changes and modifications also belong to the scope of the present invention. .

Sectional drawing which shows the CVD apparatus which concerns on 1st Embodiment of this invention. The top view of the apparatus shown in FIG. The figure which expands the upper part of the process chamber of the apparatus shown in FIG. 1, and shows the flow of gas. The timing chart which shows the gas supply pattern which concerns on 1st Embodiment of this invention. Sectional drawing which shows the process chamber of the CVD apparatus which concerns on 2nd Embodiment of this invention. The figure which expands the upper part of the process chamber of the apparatus shown in FIG. 5, and shows the flow of gas. Sectional drawing which shows the process chamber of the CVD apparatus which concerns on 3rd Embodiment of this invention. The top view of the apparatus shown in FIG. Sectional drawing which shows the processing chamber of the CVD apparatus which concerns on 4th Embodiment of this invention. Sectional drawing which shows the CVD apparatus which concerns on 5th Embodiment of this invention. The figure which expands the upper part of the processing chamber of the apparatus shown in FIG. 10, and shows the flow of gas. The timing chart which shows the gas supply pattern which concerns on 5th Embodiment of this invention. Sectional drawing which shows the process chamber of the CVD apparatus which concerns on 6th Embodiment of this invention. The figure which expands the upper part of the process chamber of the apparatus shown in FIG. 13, and shows the flow of gas. Sectional drawing which shows the process chamber of the CVD apparatus which concerns on 7th Embodiment of this invention. The top view of the apparatus shown in FIG.

Explanation of symbols

  8, 8X ... Processing chamber, 12 ... Heater, 14 ... Heat insulating material, 20 ... Wafer boat (holder), W ... Wafer, 39 ... Vacuum exhaust part (exhaust system), 42 ... Silane system gas supply system, 44 ... Nitriding Gas supply system, 46 ... hydrocarbon gas supply system, 48, 50, 52 ... gas nozzle, 53 ... supply hole, 142 ... organometallic gas supply system, 144 ... oxidizing gas supply system, 148, 150 ... gas nozzle, 153 ... supply hole .

Claims (12)

  1. A method of performing a CVD process on a plurality of substrates to be processed together in a vertical CVD apparatus,
    The device is
    An airtight processing chamber for storing the substrate to be processed;
    A holder for holding the substrates to be processed in a stacked state in the processing chamber with a space between each other;
    A heater for heating the internal atmosphere of the processing chamber;
    An exhaust system for exhausting the processing chamber;
    A supply system for supplying a processing gas into the processing chamber;
    Comprising
    The method
    A first step of adsorbing the one gas on the surface of the substrate to be processed by supplying one gas of the first and second reaction gases and stopping the other gas;
    Supplying the other gas and stopping the one gas to cause the other gas to act on the one gas adsorbed on the surface of the substrate to be processed;
    Comprising
    By repeatedly executing the first and second steps, a thin film derived from the first and second reaction gases is formed on the substrate to be processed.
    Here, the method is
    A gas having a vapor pressure of 1.33 kPa or less or a bond dissociation energy of 250 kJ / mol or less is used as the first reaction gas, and a vapor pressure of 2.66 kPa or more and a bond dissociation of 250 kJ / mol or more are used as the second reaction gas. Use gas with energy,
    The first reaction gas is supplied from the first supply hole of the supply system, which is disposed substantially at the bottom of the processing chamber, and the second reaction gas is not supplied from the first supply hole. The second reaction gas is supplied from a plurality of second supply holes of the supply system arranged in a vertical direction next to the edge of the substrate to be processed so as to substantially cover the stacked substrates to be processed. And a CVD method in which the first reaction gas is not supplied from the second supply hole.
  2.   The CVD method according to claim 1, wherein a gas having a vapor pressure of 4 kPa or more and a bond dissociation energy of 300 kJ / mol or more is used as the second reaction gas.
  3. As the first reaction gas, a gas selected from the group consisting of Ta (OC 2 H 5 ) 5 , (C 4 H 10 N) 3 Ta (NC 4 H 9 ) is used, and as the second reaction gas, The CVD method according to claim 1, wherein a gas selected from the group consisting of water vapor, O 2 , and O 3 is used.
  4. A gas selected from the group consisting of Hf [N (CH 3 ) 2 ] 4 and Hf [N (CH 3 ) (C 2 H 5 )] 4 is used as the first reaction gas, and the second reaction gas is used. The CVD method according to claim 1, wherein an oxidizing gas is used.
  5.   The CVD method according to claim 1, wherein an organometallic gas containing aluminum is used as the first reaction gas, and an oxidizing gas is used as the second reaction gas.
  6.   The CVD method according to claim 1, wherein an organometallic gas containing tantalum is used as the first reaction gas, and an oxidizing gas is used as the second reaction gas.
  7.   The supply system includes a supply pipe extending in a vertical direction next to an edge of the substrate to be processed so as to substantially cover the stacked substrates to be processed, and the second supply hole is the supply hole. The CVD method according to claim 1, further comprising holes formed in the pipe.
  8.   2. The CVD method according to claim 1, wherein the supply system includes a first inert gas line connected to the first supply hole and a second inert gas line connected to the second supply hole.
  9.   The method includes performing a first purge step between the first and second steps, performing a second purge step between the second and first steps, and the first purge step including the first purge step. While supplying the inert gas from the supply hole, the process chamber is evacuated to purge the first reaction gas from the process chamber, and the second purge step includes the inert gas from the second supply hole. The CVD method according to claim 8, further comprising: exhausting the processing chamber while purging gas and purging the second reaction gas from the processing chamber.
  10.   The CVD method according to claim 1, wherein in the first and second steps, the processing chamber is evacuated by the exhaust system.
  11.   The said 1st and 2nd supply hole is arrange | positioned at the 1st side of the said process chamber, The said exhaust system is comprised so that it may exhaust from the 2nd side of the said process chamber facing the said 1st side. The CVD method as described.
  12.   The exhaust system includes a plurality of exhaust holes arranged in a vertical direction beside an edge of the substrate to be processed so as to substantially cover the stacked substrates to be processed. The supply hole is disposed on the first side of the processing chamber, the exhaust hole is disposed on the second side of the processing chamber facing the first side, and the method includes: 2. The CVD method according to claim 1, wherein laminar flows of the first and second reaction gases are formed between the substrate to be processed by exhausting through an exhaust hole.
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